CA2011642C - Benzoxazine dyes - Google Patents
Benzoxazine dyesInfo
- Publication number
- CA2011642C CA2011642C CA002011642A CA2011642A CA2011642C CA 2011642 C CA2011642 C CA 2011642C CA 002011642 A CA002011642 A CA 002011642A CA 2011642 A CA2011642 A CA 2011642A CA 2011642 C CA2011642 C CA 2011642C
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- Prior art keywords
- hair
- dye
- compounds
- dyes
- benzoxazine
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D267/00—Heterocyclic compounds containing rings of more than six members having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D267/02—Seven-membered rings
- C07D267/08—Seven-membered rings having the hetero atoms in positions 1 and 4
- C07D267/12—Seven-membered rings having the hetero atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
- C07D267/14—Seven-membered rings having the hetero atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Coloring (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Novel nitrobenzoxazine compounds are useful as dyes for coloring keratinaceous substrates such as human hair. Compounds of formula I
(see fig. I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
(see fig. I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
Description
20116~2 BACKGROUND
The use of nitro-substituted para-phenylenediamines as dyes for keratinaceous substrates 18 well known. See J. F. Corbett, The Chemi~try of Synthetlc Dye~, Vol. V., R. Venkataraman, ed., Academic Pres~., New York, p. 475 (1971). U.S. Patents 3,591,638;
4,470,826 and 4,668,236, as well a~ Canadian Patents 806,152 and 935,094 describe the preparation and use of these type~ of dyes.
Hair dye chemi6ts have long 6earched for 6ubstitutes for some o~ the 6impler 2-nitro-~-phenylenediamine (2-NO2-PPD) derivative~, e.g. 2-nitro-E~-phenylenediamine, because of poor ~tability in cosmetic formulation~ and poor washfastne 8. However, many of the compounds ~uggested a5 substitutes for 2-NO2-PPD do not possess the unique bright orange-red color and, therefore, represent poor substitutes. Indeed it has been shown that substitution on the amino group in the 2-nitro-E~-phenylenediamine series gives absorption maxima at considerably longer wavelength.
The color of these nitro dyes is shifted towards red-violet or violet rather than orange-red (See J.F. Corbett, J. Soc. Cosmet.
Chem., 3S, 297, (1984)).
The basic structure of the target compounds is 3,4-dihydro-2H-1,4-benzoxazine. A number of approaches to the synthesis of this system have been reported since 1889.
~ a ~ 1 i 6 4 2 Work on the synthesis of 1,4-benzoxazine was reported by Knorr at Ber. 22, 2085 (1889) and Ber. 55, 3818 (1922).
Heating 2-(2-chloroethylamino)phenol 6a with alkali gave 1,4-benzoxazine 7a.
NHCH2CH2C1 HN ~
[~,OH ~ O
~ ~, Compound 7a was also synthesized from 2-(2-hydroxyethylamino)-anisole 8a under acidic condition using hydrochloric acid at 160-180~C (A. Fairbourne and H. Thomas, J. Chem. Soc., 119-2076 (1921)).
~HCH2CH20H
Hill and Ramge reported at J. Chem. Soc., 3709 (1964) a convenient synthesis of 7-methoxy-1,4-benzoxazine from 2-amino-5-methoxyphenol 9a. Compound 9a reacted with chloroacetylchloride in acetone to give 2-chloroacetamido-5-methoxy phenol lOa. An intramolecular cyclization of lOa with aqueous sodium hydroxide produced 7-methoxy-3-oxo-1,4-benzoxazine lla, which upon reduction with lithium aluminum hydride in THF resulted in the formation of 7-methoxy-3,4-dihydro-2H-1,4-benzoxazine 12a.
. , 4.~
o NH2 NHCOCH~CIHN ~l NH ~
~ OH ~ O H ~ O ~ O
OMe OMe OM~ OMc ~a lOa I la 12a In U.S. Patents 3,690,810 and 3,817,995, L'Oreal reported the synthesis of 6-hydroxy (or amino)-3,4-dihydro-2H-1,4-benzoxazine 15a (or l9a) as an oxidation coupler.
Reaction of 2-amino-4-methoxyanisole 13a with 2-bromoethanol and calcium carbonate in water gave compound 14a.
Subsequent cyclization of 4a with HBr afforded 15a.
NHl NHCH2CH20H HN ~
~[~OCH3 ~,OCH3 ~ ~
Treatment of 2-methoxy-5-nitroaniline 16a with 2-chloroethyl chloroformate and calcium carbonate in dioxaneafforded the carbamate 17a. Rearrangement of 17a followed by an intramolecular cyclization by action of potassium hydroxide in ethanol led to the formation of 6-nitrobenzoxazine 18a. Reduction of ~ with iron in acetic acid produced 6-aminobenzoxazine l9a.
NH2 NHCOOCHICHlCIHt~ ~l O~NJ~OCH~ ~OCH~ ~ O
17a18a X = NO2 ~a. X = NH~
Recently, two procedures have been reported for the synthesis of 1,4-benzoxazine systems by the use of an intramolecular reductive cyclization of nitroketones.
Condensation of 20a with benzylamine afforded phenoxy alcohol 21a, which was oxidized with Jones reagent to give the nitroketone 22a. Reductive cyclization of 22a with Raney Ni~ in ethanol afforded 23a. This was reported in Synthesis 660, 1974 by S. P. Gupta et al.
fH2NHPh CH2NHPh CH2NHPh HCOH - C--~ iC
NOt NO2 CH2 NOt CH2 HN CHt-~,OCH~--C--CH~
20a 21a 22a 23a Ph = a phenyl ring Similarly, compound 24a was converted to 25a by catalytic transfer hydrogenation using NaH2PO2 as hydrogen donor and 5~ Pd-C as catalyst in a two phase system (H2O/THF). See P. Battiston et al., Synthesis 220 (1979).
o Ph Ph--C R I ,C~
~ o R2 ~~~ c 24a 25a Ph = phenyl ~Trade-mark X
Coudert et al. reported in Synthesis, 541 (1979) a new synthetic approach to 1,4-benzoxazine using solid-liquid phase-transfer catalysis. Cyclocondensation of ortho-hydroxycarboxanilides 26a with 1,2-dibromoethane in the presence of powdered NaOH and Aliquat 336 in CH3CN/CH2CI2 proceeded in high yield to give 27a which, with KOH in MeOH, afforded NHCOR RCON ~l HN ~
~OH ~ O ~ o R2 R2 Rt 26a 271 ~
The N-substituted 1,4-benzoxazine 30a was obtained by a photochemical cyclization of 29a with irradiation (100 W
high-pressure mercury lamp). See K. Mutai et al., Tet.
Letters, 931 (1978).
N ~~
The use of nitro-substituted para-phenylenediamines as dyes for keratinaceous substrates 18 well known. See J. F. Corbett, The Chemi~try of Synthetlc Dye~, Vol. V., R. Venkataraman, ed., Academic Pres~., New York, p. 475 (1971). U.S. Patents 3,591,638;
4,470,826 and 4,668,236, as well a~ Canadian Patents 806,152 and 935,094 describe the preparation and use of these type~ of dyes.
Hair dye chemi6ts have long 6earched for 6ubstitutes for some o~ the 6impler 2-nitro-~-phenylenediamine (2-NO2-PPD) derivative~, e.g. 2-nitro-E~-phenylenediamine, because of poor ~tability in cosmetic formulation~ and poor washfastne 8. However, many of the compounds ~uggested a5 substitutes for 2-NO2-PPD do not possess the unique bright orange-red color and, therefore, represent poor substitutes. Indeed it has been shown that substitution on the amino group in the 2-nitro-E~-phenylenediamine series gives absorption maxima at considerably longer wavelength.
The color of these nitro dyes is shifted towards red-violet or violet rather than orange-red (See J.F. Corbett, J. Soc. Cosmet.
Chem., 3S, 297, (1984)).
The basic structure of the target compounds is 3,4-dihydro-2H-1,4-benzoxazine. A number of approaches to the synthesis of this system have been reported since 1889.
~ a ~ 1 i 6 4 2 Work on the synthesis of 1,4-benzoxazine was reported by Knorr at Ber. 22, 2085 (1889) and Ber. 55, 3818 (1922).
Heating 2-(2-chloroethylamino)phenol 6a with alkali gave 1,4-benzoxazine 7a.
NHCH2CH2C1 HN ~
[~,OH ~ O
~ ~, Compound 7a was also synthesized from 2-(2-hydroxyethylamino)-anisole 8a under acidic condition using hydrochloric acid at 160-180~C (A. Fairbourne and H. Thomas, J. Chem. Soc., 119-2076 (1921)).
~HCH2CH20H
Hill and Ramge reported at J. Chem. Soc., 3709 (1964) a convenient synthesis of 7-methoxy-1,4-benzoxazine from 2-amino-5-methoxyphenol 9a. Compound 9a reacted with chloroacetylchloride in acetone to give 2-chloroacetamido-5-methoxy phenol lOa. An intramolecular cyclization of lOa with aqueous sodium hydroxide produced 7-methoxy-3-oxo-1,4-benzoxazine lla, which upon reduction with lithium aluminum hydride in THF resulted in the formation of 7-methoxy-3,4-dihydro-2H-1,4-benzoxazine 12a.
. , 4.~
o NH2 NHCOCH~CIHN ~l NH ~
~ OH ~ O H ~ O ~ O
OMe OMe OM~ OMc ~a lOa I la 12a In U.S. Patents 3,690,810 and 3,817,995, L'Oreal reported the synthesis of 6-hydroxy (or amino)-3,4-dihydro-2H-1,4-benzoxazine 15a (or l9a) as an oxidation coupler.
Reaction of 2-amino-4-methoxyanisole 13a with 2-bromoethanol and calcium carbonate in water gave compound 14a.
Subsequent cyclization of 4a with HBr afforded 15a.
NHl NHCH2CH20H HN ~
~[~OCH3 ~,OCH3 ~ ~
Treatment of 2-methoxy-5-nitroaniline 16a with 2-chloroethyl chloroformate and calcium carbonate in dioxaneafforded the carbamate 17a. Rearrangement of 17a followed by an intramolecular cyclization by action of potassium hydroxide in ethanol led to the formation of 6-nitrobenzoxazine 18a. Reduction of ~ with iron in acetic acid produced 6-aminobenzoxazine l9a.
NH2 NHCOOCHICHlCIHt~ ~l O~NJ~OCH~ ~OCH~ ~ O
17a18a X = NO2 ~a. X = NH~
Recently, two procedures have been reported for the synthesis of 1,4-benzoxazine systems by the use of an intramolecular reductive cyclization of nitroketones.
Condensation of 20a with benzylamine afforded phenoxy alcohol 21a, which was oxidized with Jones reagent to give the nitroketone 22a. Reductive cyclization of 22a with Raney Ni~ in ethanol afforded 23a. This was reported in Synthesis 660, 1974 by S. P. Gupta et al.
fH2NHPh CH2NHPh CH2NHPh HCOH - C--~ iC
NOt NO2 CH2 NOt CH2 HN CHt-~,OCH~--C--CH~
20a 21a 22a 23a Ph = a phenyl ring Similarly, compound 24a was converted to 25a by catalytic transfer hydrogenation using NaH2PO2 as hydrogen donor and 5~ Pd-C as catalyst in a two phase system (H2O/THF). See P. Battiston et al., Synthesis 220 (1979).
o Ph Ph--C R I ,C~
~ o R2 ~~~ c 24a 25a Ph = phenyl ~Trade-mark X
Coudert et al. reported in Synthesis, 541 (1979) a new synthetic approach to 1,4-benzoxazine using solid-liquid phase-transfer catalysis. Cyclocondensation of ortho-hydroxycarboxanilides 26a with 1,2-dibromoethane in the presence of powdered NaOH and Aliquat 336 in CH3CN/CH2CI2 proceeded in high yield to give 27a which, with KOH in MeOH, afforded NHCOR RCON ~l HN ~
~OH ~ O ~ o R2 R2 Rt 26a 271 ~
The N-substituted 1,4-benzoxazine 30a was obtained by a photochemical cyclization of 29a with irradiation (100 W
high-pressure mercury lamp). See K. Mutai et al., Tet.
Letters, 931 (1978).
N ~~
2 0[~O(CH2)"NHR ~ ~
29a }Ih In U.S. Patent 4,552,951, an azo dye was prepared using benzomorpholine couplers and having one or two cinnamoyl substituents. At column 2, lines 37 and 57, NO2 and NH2 are disclosed as substituents on the benzene ring of the bicyclic benzoxazine system.
Chemical Abstracts 106: 138457t discloses herbicidal compositions containing benzoxazine derivatives.
~ .
Chemical Abstracts 106: 102305c recites 7,8--difluoro-3,4-dihydro-3-methyl-2H-1,4-benzoxazine as a herbicide.
While various of these references show compounds which are similar to the structural formulas recited herein, none of them actually teaches the use of applicants' compounds as dyes.
T~F INVENTION
It has been discovered that certain benzo-heterocyclic compounds are useful as direct dyes for coloring keratinaceous fibers, e.g., human or other hair.
The compounds of the invention conform to formula I:
X--N (CH2)~
02N~
NH--Y
wherein: X and Y are independently selected from the group consisting of: hydrogen, Cl-6 alkyl, Cl-6 alkoxyalkyl, and Cl-6 aminoalkyl, C16 hydroxyalkyl, and C16 hydroxyaminoalkyl; and m = 1, 2, or 3.
'- 2Ul1642 These compound~ are novel dyes and are produced via chemical reactions such as those discussed above and 6et out in the examples.
We have found that the benzoxazine derivatives of the current invention (e.g. thosQ of structurQ I), while analogs of 2-nitro-~-phenylenediamine and highly substituted, ~till have absorption maxima in the orange-red region of the spectrum and are, therefore, excellent substitutes for 2-nitro-~-phenylenediamine.
In addition, we have found that they show excellent washfastness (i.e., to normal shampooing).
The invention concerns the novel compounds and methods of using same.
ADVANTAGES
The compounds and methods of the invention have several advantages over other systems used in the art.
Specifically, each compound can be used to replace a specific nitroparaphenylenediamine, and the benzoxazines often are superior in washfastness to other nitro-paraphenylene diamines, so that the color remains on the treated or dyed substrate through a larger number of washinge.
While 2-nitro-~-phenylenediamine undergoes ready nucleophilic sub6titution of amino groups by monoethanolamine in aqueous system (M. Bil and J. F. Corbett, Dyes and Pigments 2,215, 1981), the new dye, e.g. 7, suffers from little amine exchange. This will improve the storage stability of dye formulations.
These and other advantages and aspects of the invention will be better understood after consideration of the following description and claims.
DESCRIPTION OF THE INVENTION
The invention will be described in terms of the compounds and their preparation, as well as in terms of the compositions and methods which use them and the substrates which are colored thereby.
Unless stated otherwise, all percentages stated herein are weight percent (wt.~), based on total composition weight.
COMPOUNDS
The compounds of the invention conform generally to formula I:
X--N ICH2)m ~
02N ~
NH--Y
wherein: X and Y are independently selected from the group consisting of: hydrogen, Cl-6 alkyl, Cl-6 alkoxyalkyl, and Cl-6 amino-alkyl, Cl6 hydroxyalkyl, and Cl6 hydroxy-aminoalkyl;
and m = 1, 2, or 3.
Preferred compounds are those conforming to formula II:
Rl--11 (CH2)p ~ o . II
~ ~ d ~
wherein:
p = 1, 2, or 3; and R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1C(OH)c, wherein n = 1-6 and c=0-3.
Useful compounds include, but are not limited to:
A. 7-Amino-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
B. 7-Amino-4-methyl-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
C. 7-Amino-4-ethyl-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
D. 7-Amino-4-(2-hydroxyethyl)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
E. 7-Amino-4-(2,3-dihydroxypropyl)-6-nitro-3,4-dihydro-1,4-benzoxazine;
F. 7-(2-Hydroxyethylamino)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine; and H. 4-(2-Hydroxyethyl)-7-(2-hydroxyethylamino)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine.
~ 2 ~
Highly preferred compound~ are those conforming to formula II, in which p=2. compounds of formula II in which Rl and R2 are either hydrogen, Cl_6 alkyl, or, with CnH2n~1_c(OH)c,with n and c being as defined above, are among the highly preferred compounds. The most preferred compounds arel A, D, F, and H, above.
Mixtures of compounds of formula I with each other and other colorants are contemplated.
PREPARATION OF COMPOUNDS
The preparation of compounds of the invention involve~ a series of chemical reactions which are each individually known. Compounds of formula I can be prepared by four routes shown in Schemes I, II, III and IV in Example 1.
Detailed Description of the Invention The direct dyes of the present invention are suitable for incorporation in hair dye- or surface active agent-containing compositions comprising one or more of the following: solvents, surfactants or surface-actiVe agent8, thickeners, antioxidant~, preservatives, fragrance8, and other constituent8 typically employed in hair dye compositions.
In addition, as was mentioned above, dye compositions may also contain one or more additional dye component(s), the admixture of dyes (including the dye of the present invention) providing the desired shade.
~B
' ' ~'f 20116~2 The compo~itions of the present invention may al60 contaln one or more hair conditioning agents. Such conditioning agent~ are typically cationic in character and include catlonic sUrface-active agents and cationic polymeric material~. The dyes of the present lnvention might also be incorporated into an oxidation dye basQ, to obtain a desired shade.
The constituents includable in the hair dye compositions of the pre~ent invention are generally within the ranges set out below.
TABLE
Broad Range Preferred Range Constituents Wt. % Wt. %
Dyes of the invention 0.001-5 0.01-1 Other dyes 0-10 0.01-4 Surfactant5 0-25 0.1-5 Thickening agents 0-20 0.1-5 Nonaqueous solvent(s) 0-40 1-10 pH Modifiers 0-20 0.05-5 Fragrance 0-5 0.05-1 Water q. 8 . 100 q. 8. 100 ~ ~ 2011~2 In practice, the dyes employed in this invention will generally be used with other dyes. The amount o~ the dyes used would depend on the lightness or darkness of the desired shade, as well as on the desired tonality.
In carrying out the pre8ent invention, any of the nitrobenzoxazine dyes described above, or combinationB thereof, are incorporated in a fluid hair dye vehicle of the type 8uitable for applying direct-dyeing dyes. A
large number of such vehicle8 are known to those in this art. These may vary fro~ simple aqueous ~olution8 and/or suspensions of the dye to very sophisticated aqueous compositions such as creams, mousses, lotions, pastes, gels, and the like. Often, the compositlons of the present invention contain, in addition to the sub~ect dyes herein disclosed, a second dye or a blend of other dyes, nonionic and anionic surfactants, solvents, thickeners, antioxidants, preservatives, fragrances, etc. In these aqueous compositions, the carriers or vehicles may be water or a combination of water with other solvents, e.g., ethanol. The dyes may also be employed in aerosol systems, e.g., an aerosol emulsion system in which the dye is contained in an agueous phase o~ the system. See, for example, U.S. 4,021,486 to Halasz, et al.
O ~16 4 2 The nitrobenzoxazine dyes employed in the present inventlon can be employed to prepare basic, neutral or acidic dye compositlons.
Furthermore, they may be included in hair dyeing compositions which contain other direct dyeing dyes. A variety of the direct dyeing colorants known in the prior art are useful for this purpose. They include nitro dyes, azo dyes, anthraquinone dyes, etc.
By way of illustration, any of the nitro dyes disclosed in the ~ollowing U.S. Patent5 may be used in con~unction with the present dyes:
U.S. Pat. Nos: 2,7S0,326; 2,750,327; 3,088,877; 3,088,878; 3,088,978;
3,642,423; 3,950,127; 4,125,601; 4,432,769, and 4,337,061.
The pH of the present dye compositions can vary from about 4 to about 12 and preferably from about 7 to about 11.5, and may be obtained by ad~ustment with a suitable pH modifylng agent. The compositions herein may also contain buffering agents which maintain the pH within a particular range.
When the compositions are preferably to be basic, an alkalizing agent can be employed over a wide range, depending on the dye and particular alkalizing agent employed and the desired pH. Illustratively, the alkalizing agent can vary between about 0 and about 20%, preferably from about O.OS to about 5%, and most preferably from about 0.10 to about 2%, by weight of the composition. Any of a wide variety of alkalizing agents can be used to adjust the pH of the present dyeing composition on the basic si~e.
? ~011~2 Ammonium hydroxide or aqueous ammonia, because of its freedom from toxicity over a wide concentration range and its economy, is an acceptable alkalizing agent. However, there can be used a8 an alkalizlng agent, in place of, or together with, ammonia, any other compatible amine or ammonia derivative such a8 an alkylamine, e.g., ethylamine, dipropylamine, or triethylamine; an alkanediamine, e.g., 1,3-diaminopropane; an alkanola~ine, e.g., monoethanolamine or diethanolamine, triethanolamine, a polyalkylene polyamine, e.g., diethylenetriamine; or a heterocyclic amine, such as ~orpholine. Mixtures can be used.
The pH of the composition may be ad~usted on the acid side with any inorganic or organic acid or acid salt which is compatlble with the composit~on and will not introduce toxicity under it~ conditions of use, especially when acid compositions are desired. Illustrative of acids or acid ~alts there can be mentioned are: sulfuric, formic, acetic, oleic, lactic, citric or tartaric acid, or ammonium sulfate, sodium dihydrogen phosphate or potassium bisulfate. Illustratively, the amount of acidifying agent present is from about 0 to about 5%, and preferably from about 0.05 to about 1%.
The alkalizing, acidifying and buffering agents discussed herein are referred to as "pH modifiersn.
f~ 11642 Surface active agents can also be employed ln the dyeing compositions of this invention. The~e can be anionic, nonionic or cationic. By way of example of the various types of surface active agent~, there can be mentioned: higher alXylbenzene 8Ulfonates; alXylnaphthalenesulfonates;
sulfonated esters of alcohol8 and polyba8ic acld8; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols alkyldimethylbenzylammonium chlorides, salts of fatty acids or fatty acid mixtures; N-oxyalkylated fatty acid alkanolamides, and the like.
Illustrative of specific surfactant8 that can be mentioned are:
sodium lauryl sulfate; polyoxyethylene lauryl ester; myristyl sulfate;
glyceryl monstearate; triethanolamine oleate, the sodium 6alt of palmitic methyl taurine; cetyl pyridinium chloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide; polyoxyethylene stearate; ethoxylated oleyl diethanolamide; polyethylene glycol amide8 of hydrogenated tallow;
stearyldimethylbenzyl ammonium chloride; dodecylbenzene 80dium sulfonate;
2-amino-2-methyl propanol; the triethanolamine salt of p-dodecylbenzene sulfonate; the triethanolamine salt of p-dodecylbenzene sulfonate;
nonylnaphthalene sodium sulfonate; dioctyl sodium sulfo5uccinate; sodium N-methyl-N-oleoyl taurate; the oleic acid ester of sodium isethionate;
sodium dodecyl sulfate; the sodium salt of 3-0-diethyl tridecanol-6-sulfate and the like.
The quantity of surface active agent can vary over a wide range, such as that of from about 0.05% to about 15%, and preferably from about 0.10 to about 5%, by weight of the composition.
1 i! B ~ ~
A thickening agent may also be incorporated in the dyeing compositionsof this invention. It may be one or ~everal of those commonly used in hair dyeing. These are exemplified by 8uch things as sodium alginate or gum arabic, or cellulose derlvatives, such as methylcellulose, e.g., Methocel 60HG, or the sodium salt of carboxymethylcellulose, or hydroxyethyl-cellUlOse, e.g., Cello5ize QP-40 or acrylic polymers, such as polyacryllc acid sodiUm salt, or inorganic thickeners, such as bentonite.
Mixtures are operable.
The quantity of thickening agent can al80 vary over a wide range, such a~ that of from about 0.1 to about 20%. Ordinarily, the thickenlng agent concentration will range from about O.S to 5% by weight of the total composition. The viscosity of the compo8ition may vary from about 1 cp to about 100,000 cps. For a typical lotion formulation, composition viscosity i8 between about 100 cps to about 10,000 Cp8.
It is also useful to incorporate an antloxidant in the present dye compositions. A variety of antioxidants are known in the prior art which would be useful for this purpose. Among these, mention may be made of the inorganic sulfites~ e.g., 60dium 8ulfite, thioglycollic acid and other mercaptans, butylated hydroxytoluene, sodium dithionite, various forms of ascorbic acid and its derivatives, e.g., sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, etc.
The quantity of antioxidant, when used, can vary quite a bit.
However, this will, in general, be on the order of about 0.001 to 1% by weight.
*Trademarks -16-The nitrobenzoxazine dyes are incorporated in co~positions of this lnvention in tinctorially ef~ectiv~ quantltie~, i.e., in concentrations which are adequate to color the hair. These quantities can vary over a wlde range, but ordinarily they wlll constitute from about 0.001 to greater than about S%, e.g., 10%, by wQight o~ the compo~ition. However, the quantity will preferably be from about 0.05 to about 2%, most preferably about 0.1 to about 2 wt. %, o~ the compo~ition.
The ma~or con6tituent of the composition employed i8 usually water, and this can vary in amount over a wid~ range dependent in large measure on the quantity of other additives. Thus, the water content can be as little as 10%, but preferably will amount to from about 70 to 99% by weight of the composition.
The dyeing compositions o~ this invention are preferably aqueous compositions. The term ~aqueous composition" is used herein in its usual generic sense as embraclng any water-containing composition useful for the present purposes. This includes true solutions of the dye in an aqueous medium, either alone or in con~unction with other materials, which are also dissolved or dispersed ln the aqueous medium. The term "aqueous composition" also emcompasses any mixture of dye with the aqueous medlum, either alone or together with other ingredients. The dye may be colloidally dispersed in the medium or may merely be intimately mixed therein.
(~) f 2011642 Moreover, the aqueous medlum may comprlse water or water and an additional or auxillary 601vent. The latter may be employed as a common solvent to enhance the 801ubillty of the dye or 60me other organic material. Other auxiliary sOlVents which may be used for this purpo6e include ethanol, carbitol, i80propanol, propylens glycol, ethylene glycol, dlethylene glycol, diethylene glycol monoethyl ether, glycerine, and the llke and mixtures thereof.
The nitrobenzoxazine dye(s) and any of the surface active agents, thickening agents, and combinations thereof 6et forth above may be used in the proportions specified in the Table I.
The aqueous dyeing compositions of this invention can be prepared by the conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or sU6pending the dye in water in the desired concentrations. Water miscible organic solvents, such as aliphatic Cl_4 alcohols, eg., ethanol or glycol ethers, can be employed to facilitate solution of the dye. In one process, the dye can be dissolved first in the solvent and this solution then diluted with water.
The di6per~ion of the various ingredients can also be facilitated by heating the composition at temperatures varying from about 40-C to about llO-C, either before dilution with water or afterwards. The concentrations of co-solvents or diluents will be from about 5% to about 95%, depending upon 6torage, handling, and application considerations.
-(~ 20116~2 The colorant~ of the inventlon may be u~ed in combination with oxidation dye~. The compounds of formula I are used ~or the purpose of highlighting the flnal dyeing. These composition8 contain at least one direct dye of formula I and oxidation dye precursors consisting of developers and couplers well-known in the hair-coloring art (e.g.
p-phenylenediamines, m-phenylenediamines, resorcinol). The concentration of dye precursor~ ranges from about 0.001 to about 5% by weight.
In use, the dys mixture is mixed with hydrogen peroxide solution (about 0.1 to about 10% w/w/) immediately prior to application to the hair.
The colorant~ of the invention can also be used in combination with other direct dyes, such as azo, anthraquinone and nitro dyes, in a process of direct dyeing of hair. The concentration of these other dyes ranges from about 0.001 to about 5% by weight.
Other conventional additives, ie, excipients (eg., perfumes, thickeners, surfactants, stabilizers), and the like can be beneficially employed in the compositions o~ the invention. When present, they will be used in quantities ranging from about 0.5 to about 55 wt. %.
The compounds of the invention are useful in variou~ conventional methods of coloring keratinaceou~ substrates. Accordlngly, the substrates may be contacted with the color-containing formulations via dipping, spraying, painting, dabbing, application of gels, mou#ses, powders, etc.
When applied to living hair on the human head, the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as pouring the compo8ition directly onto the hair until saturated.
The reaction time, or time of contact of the dyeing composition with the hair, i8 not critical and can vary over a wide range used in the hair dyeing art, suCh as periods of about 5 minutes to about 2 hours.
Preferably, a period of from about 5 minutes to about 60 minutes i8 utilized, and most often a period of about 20 to about 40 minutes.
The dyeing temperature can vary over wide limits as is conventional ln the art. Thus, the dyeing temperature can vary from about room temperature, e.g., about 20- to about 60-C, and preferably from about 20-to about 45-C. At the end of the time period, the composition is rinsed from the hair with water, although a weak acid solution may be employed as the rinse.
(~, (? 2011642 One preferred sequence of steps by which colorant formulatlons in accordance with the invention are contacted with human hair involves:
(1) Mix or otherwise prepare dyeing ~olution with oxidant, if ~ppropriate.
(2) Apply developer to the hair.
(3) Rinse.
(4) Shampoo.
29a }Ih In U.S. Patent 4,552,951, an azo dye was prepared using benzomorpholine couplers and having one or two cinnamoyl substituents. At column 2, lines 37 and 57, NO2 and NH2 are disclosed as substituents on the benzene ring of the bicyclic benzoxazine system.
Chemical Abstracts 106: 138457t discloses herbicidal compositions containing benzoxazine derivatives.
~ .
Chemical Abstracts 106: 102305c recites 7,8--difluoro-3,4-dihydro-3-methyl-2H-1,4-benzoxazine as a herbicide.
While various of these references show compounds which are similar to the structural formulas recited herein, none of them actually teaches the use of applicants' compounds as dyes.
T~F INVENTION
It has been discovered that certain benzo-heterocyclic compounds are useful as direct dyes for coloring keratinaceous fibers, e.g., human or other hair.
The compounds of the invention conform to formula I:
X--N (CH2)~
02N~
NH--Y
wherein: X and Y are independently selected from the group consisting of: hydrogen, Cl-6 alkyl, Cl-6 alkoxyalkyl, and Cl-6 aminoalkyl, C16 hydroxyalkyl, and C16 hydroxyaminoalkyl; and m = 1, 2, or 3.
'- 2Ul1642 These compound~ are novel dyes and are produced via chemical reactions such as those discussed above and 6et out in the examples.
We have found that the benzoxazine derivatives of the current invention (e.g. thosQ of structurQ I), while analogs of 2-nitro-~-phenylenediamine and highly substituted, ~till have absorption maxima in the orange-red region of the spectrum and are, therefore, excellent substitutes for 2-nitro-~-phenylenediamine.
In addition, we have found that they show excellent washfastness (i.e., to normal shampooing).
The invention concerns the novel compounds and methods of using same.
ADVANTAGES
The compounds and methods of the invention have several advantages over other systems used in the art.
Specifically, each compound can be used to replace a specific nitroparaphenylenediamine, and the benzoxazines often are superior in washfastness to other nitro-paraphenylene diamines, so that the color remains on the treated or dyed substrate through a larger number of washinge.
While 2-nitro-~-phenylenediamine undergoes ready nucleophilic sub6titution of amino groups by monoethanolamine in aqueous system (M. Bil and J. F. Corbett, Dyes and Pigments 2,215, 1981), the new dye, e.g. 7, suffers from little amine exchange. This will improve the storage stability of dye formulations.
These and other advantages and aspects of the invention will be better understood after consideration of the following description and claims.
DESCRIPTION OF THE INVENTION
The invention will be described in terms of the compounds and their preparation, as well as in terms of the compositions and methods which use them and the substrates which are colored thereby.
Unless stated otherwise, all percentages stated herein are weight percent (wt.~), based on total composition weight.
COMPOUNDS
The compounds of the invention conform generally to formula I:
X--N ICH2)m ~
02N ~
NH--Y
wherein: X and Y are independently selected from the group consisting of: hydrogen, Cl-6 alkyl, Cl-6 alkoxyalkyl, and Cl-6 amino-alkyl, Cl6 hydroxyalkyl, and Cl6 hydroxy-aminoalkyl;
and m = 1, 2, or 3.
Preferred compounds are those conforming to formula II:
Rl--11 (CH2)p ~ o . II
~ ~ d ~
wherein:
p = 1, 2, or 3; and R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1C(OH)c, wherein n = 1-6 and c=0-3.
Useful compounds include, but are not limited to:
A. 7-Amino-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
B. 7-Amino-4-methyl-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
C. 7-Amino-4-ethyl-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
D. 7-Amino-4-(2-hydroxyethyl)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine;
E. 7-Amino-4-(2,3-dihydroxypropyl)-6-nitro-3,4-dihydro-1,4-benzoxazine;
F. 7-(2-Hydroxyethylamino)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine; and H. 4-(2-Hydroxyethyl)-7-(2-hydroxyethylamino)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine.
~ 2 ~
Highly preferred compound~ are those conforming to formula II, in which p=2. compounds of formula II in which Rl and R2 are either hydrogen, Cl_6 alkyl, or, with CnH2n~1_c(OH)c,with n and c being as defined above, are among the highly preferred compounds. The most preferred compounds arel A, D, F, and H, above.
Mixtures of compounds of formula I with each other and other colorants are contemplated.
PREPARATION OF COMPOUNDS
The preparation of compounds of the invention involve~ a series of chemical reactions which are each individually known. Compounds of formula I can be prepared by four routes shown in Schemes I, II, III and IV in Example 1.
Detailed Description of the Invention The direct dyes of the present invention are suitable for incorporation in hair dye- or surface active agent-containing compositions comprising one or more of the following: solvents, surfactants or surface-actiVe agent8, thickeners, antioxidant~, preservatives, fragrance8, and other constituent8 typically employed in hair dye compositions.
In addition, as was mentioned above, dye compositions may also contain one or more additional dye component(s), the admixture of dyes (including the dye of the present invention) providing the desired shade.
~B
' ' ~'f 20116~2 The compo~itions of the present invention may al60 contaln one or more hair conditioning agents. Such conditioning agent~ are typically cationic in character and include catlonic sUrface-active agents and cationic polymeric material~. The dyes of the present lnvention might also be incorporated into an oxidation dye basQ, to obtain a desired shade.
The constituents includable in the hair dye compositions of the pre~ent invention are generally within the ranges set out below.
TABLE
Broad Range Preferred Range Constituents Wt. % Wt. %
Dyes of the invention 0.001-5 0.01-1 Other dyes 0-10 0.01-4 Surfactant5 0-25 0.1-5 Thickening agents 0-20 0.1-5 Nonaqueous solvent(s) 0-40 1-10 pH Modifiers 0-20 0.05-5 Fragrance 0-5 0.05-1 Water q. 8 . 100 q. 8. 100 ~ ~ 2011~2 In practice, the dyes employed in this invention will generally be used with other dyes. The amount o~ the dyes used would depend on the lightness or darkness of the desired shade, as well as on the desired tonality.
In carrying out the pre8ent invention, any of the nitrobenzoxazine dyes described above, or combinationB thereof, are incorporated in a fluid hair dye vehicle of the type 8uitable for applying direct-dyeing dyes. A
large number of such vehicle8 are known to those in this art. These may vary fro~ simple aqueous ~olution8 and/or suspensions of the dye to very sophisticated aqueous compositions such as creams, mousses, lotions, pastes, gels, and the like. Often, the compositlons of the present invention contain, in addition to the sub~ect dyes herein disclosed, a second dye or a blend of other dyes, nonionic and anionic surfactants, solvents, thickeners, antioxidants, preservatives, fragrances, etc. In these aqueous compositions, the carriers or vehicles may be water or a combination of water with other solvents, e.g., ethanol. The dyes may also be employed in aerosol systems, e.g., an aerosol emulsion system in which the dye is contained in an agueous phase o~ the system. See, for example, U.S. 4,021,486 to Halasz, et al.
O ~16 4 2 The nitrobenzoxazine dyes employed in the present inventlon can be employed to prepare basic, neutral or acidic dye compositlons.
Furthermore, they may be included in hair dyeing compositions which contain other direct dyeing dyes. A variety of the direct dyeing colorants known in the prior art are useful for this purpose. They include nitro dyes, azo dyes, anthraquinone dyes, etc.
By way of illustration, any of the nitro dyes disclosed in the ~ollowing U.S. Patent5 may be used in con~unction with the present dyes:
U.S. Pat. Nos: 2,7S0,326; 2,750,327; 3,088,877; 3,088,878; 3,088,978;
3,642,423; 3,950,127; 4,125,601; 4,432,769, and 4,337,061.
The pH of the present dye compositions can vary from about 4 to about 12 and preferably from about 7 to about 11.5, and may be obtained by ad~ustment with a suitable pH modifylng agent. The compositions herein may also contain buffering agents which maintain the pH within a particular range.
When the compositions are preferably to be basic, an alkalizing agent can be employed over a wide range, depending on the dye and particular alkalizing agent employed and the desired pH. Illustratively, the alkalizing agent can vary between about 0 and about 20%, preferably from about O.OS to about 5%, and most preferably from about 0.10 to about 2%, by weight of the composition. Any of a wide variety of alkalizing agents can be used to adjust the pH of the present dyeing composition on the basic si~e.
? ~011~2 Ammonium hydroxide or aqueous ammonia, because of its freedom from toxicity over a wide concentration range and its economy, is an acceptable alkalizing agent. However, there can be used a8 an alkalizlng agent, in place of, or together with, ammonia, any other compatible amine or ammonia derivative such a8 an alkylamine, e.g., ethylamine, dipropylamine, or triethylamine; an alkanediamine, e.g., 1,3-diaminopropane; an alkanola~ine, e.g., monoethanolamine or diethanolamine, triethanolamine, a polyalkylene polyamine, e.g., diethylenetriamine; or a heterocyclic amine, such as ~orpholine. Mixtures can be used.
The pH of the composition may be ad~usted on the acid side with any inorganic or organic acid or acid salt which is compatlble with the composit~on and will not introduce toxicity under it~ conditions of use, especially when acid compositions are desired. Illustrative of acids or acid ~alts there can be mentioned are: sulfuric, formic, acetic, oleic, lactic, citric or tartaric acid, or ammonium sulfate, sodium dihydrogen phosphate or potassium bisulfate. Illustratively, the amount of acidifying agent present is from about 0 to about 5%, and preferably from about 0.05 to about 1%.
The alkalizing, acidifying and buffering agents discussed herein are referred to as "pH modifiersn.
f~ 11642 Surface active agents can also be employed ln the dyeing compositions of this invention. The~e can be anionic, nonionic or cationic. By way of example of the various types of surface active agent~, there can be mentioned: higher alXylbenzene 8Ulfonates; alXylnaphthalenesulfonates;
sulfonated esters of alcohol8 and polyba8ic acld8; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols alkyldimethylbenzylammonium chlorides, salts of fatty acids or fatty acid mixtures; N-oxyalkylated fatty acid alkanolamides, and the like.
Illustrative of specific surfactant8 that can be mentioned are:
sodium lauryl sulfate; polyoxyethylene lauryl ester; myristyl sulfate;
glyceryl monstearate; triethanolamine oleate, the sodium 6alt of palmitic methyl taurine; cetyl pyridinium chloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide; polyoxyethylene stearate; ethoxylated oleyl diethanolamide; polyethylene glycol amide8 of hydrogenated tallow;
stearyldimethylbenzyl ammonium chloride; dodecylbenzene 80dium sulfonate;
2-amino-2-methyl propanol; the triethanolamine salt of p-dodecylbenzene sulfonate; the triethanolamine salt of p-dodecylbenzene sulfonate;
nonylnaphthalene sodium sulfonate; dioctyl sodium sulfo5uccinate; sodium N-methyl-N-oleoyl taurate; the oleic acid ester of sodium isethionate;
sodium dodecyl sulfate; the sodium salt of 3-0-diethyl tridecanol-6-sulfate and the like.
The quantity of surface active agent can vary over a wide range, such as that of from about 0.05% to about 15%, and preferably from about 0.10 to about 5%, by weight of the composition.
1 i! B ~ ~
A thickening agent may also be incorporated in the dyeing compositionsof this invention. It may be one or ~everal of those commonly used in hair dyeing. These are exemplified by 8uch things as sodium alginate or gum arabic, or cellulose derlvatives, such as methylcellulose, e.g., Methocel 60HG, or the sodium salt of carboxymethylcellulose, or hydroxyethyl-cellUlOse, e.g., Cello5ize QP-40 or acrylic polymers, such as polyacryllc acid sodiUm salt, or inorganic thickeners, such as bentonite.
Mixtures are operable.
The quantity of thickening agent can al80 vary over a wide range, such a~ that of from about 0.1 to about 20%. Ordinarily, the thickenlng agent concentration will range from about O.S to 5% by weight of the total composition. The viscosity of the compo8ition may vary from about 1 cp to about 100,000 cps. For a typical lotion formulation, composition viscosity i8 between about 100 cps to about 10,000 Cp8.
It is also useful to incorporate an antloxidant in the present dye compositions. A variety of antioxidants are known in the prior art which would be useful for this purpose. Among these, mention may be made of the inorganic sulfites~ e.g., 60dium 8ulfite, thioglycollic acid and other mercaptans, butylated hydroxytoluene, sodium dithionite, various forms of ascorbic acid and its derivatives, e.g., sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, etc.
The quantity of antioxidant, when used, can vary quite a bit.
However, this will, in general, be on the order of about 0.001 to 1% by weight.
*Trademarks -16-The nitrobenzoxazine dyes are incorporated in co~positions of this lnvention in tinctorially ef~ectiv~ quantltie~, i.e., in concentrations which are adequate to color the hair. These quantities can vary over a wlde range, but ordinarily they wlll constitute from about 0.001 to greater than about S%, e.g., 10%, by wQight o~ the compo~ition. However, the quantity will preferably be from about 0.05 to about 2%, most preferably about 0.1 to about 2 wt. %, o~ the compo~ition.
The ma~or con6tituent of the composition employed i8 usually water, and this can vary in amount over a wid~ range dependent in large measure on the quantity of other additives. Thus, the water content can be as little as 10%, but preferably will amount to from about 70 to 99% by weight of the composition.
The dyeing compositions o~ this invention are preferably aqueous compositions. The term ~aqueous composition" is used herein in its usual generic sense as embraclng any water-containing composition useful for the present purposes. This includes true solutions of the dye in an aqueous medium, either alone or in con~unction with other materials, which are also dissolved or dispersed ln the aqueous medium. The term "aqueous composition" also emcompasses any mixture of dye with the aqueous medlum, either alone or together with other ingredients. The dye may be colloidally dispersed in the medium or may merely be intimately mixed therein.
(~) f 2011642 Moreover, the aqueous medlum may comprlse water or water and an additional or auxillary 601vent. The latter may be employed as a common solvent to enhance the 801ubillty of the dye or 60me other organic material. Other auxiliary sOlVents which may be used for this purpo6e include ethanol, carbitol, i80propanol, propylens glycol, ethylene glycol, dlethylene glycol, diethylene glycol monoethyl ether, glycerine, and the llke and mixtures thereof.
The nitrobenzoxazine dye(s) and any of the surface active agents, thickening agents, and combinations thereof 6et forth above may be used in the proportions specified in the Table I.
The aqueous dyeing compositions of this invention can be prepared by the conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or sU6pending the dye in water in the desired concentrations. Water miscible organic solvents, such as aliphatic Cl_4 alcohols, eg., ethanol or glycol ethers, can be employed to facilitate solution of the dye. In one process, the dye can be dissolved first in the solvent and this solution then diluted with water.
The di6per~ion of the various ingredients can also be facilitated by heating the composition at temperatures varying from about 40-C to about llO-C, either before dilution with water or afterwards. The concentrations of co-solvents or diluents will be from about 5% to about 95%, depending upon 6torage, handling, and application considerations.
-(~ 20116~2 The colorant~ of the inventlon may be u~ed in combination with oxidation dye~. The compounds of formula I are used ~or the purpose of highlighting the flnal dyeing. These composition8 contain at least one direct dye of formula I and oxidation dye precursors consisting of developers and couplers well-known in the hair-coloring art (e.g.
p-phenylenediamines, m-phenylenediamines, resorcinol). The concentration of dye precursor~ ranges from about 0.001 to about 5% by weight.
In use, the dys mixture is mixed with hydrogen peroxide solution (about 0.1 to about 10% w/w/) immediately prior to application to the hair.
The colorant~ of the invention can also be used in combination with other direct dyes, such as azo, anthraquinone and nitro dyes, in a process of direct dyeing of hair. The concentration of these other dyes ranges from about 0.001 to about 5% by weight.
Other conventional additives, ie, excipients (eg., perfumes, thickeners, surfactants, stabilizers), and the like can be beneficially employed in the compositions o~ the invention. When present, they will be used in quantities ranging from about 0.5 to about 55 wt. %.
The compounds of the invention are useful in variou~ conventional methods of coloring keratinaceou~ substrates. Accordlngly, the substrates may be contacted with the color-containing formulations via dipping, spraying, painting, dabbing, application of gels, mou#ses, powders, etc.
When applied to living hair on the human head, the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as pouring the compo8ition directly onto the hair until saturated.
The reaction time, or time of contact of the dyeing composition with the hair, i8 not critical and can vary over a wide range used in the hair dyeing art, suCh as periods of about 5 minutes to about 2 hours.
Preferably, a period of from about 5 minutes to about 60 minutes i8 utilized, and most often a period of about 20 to about 40 minutes.
The dyeing temperature can vary over wide limits as is conventional ln the art. Thus, the dyeing temperature can vary from about room temperature, e.g., about 20- to about 60-C, and preferably from about 20-to about 45-C. At the end of the time period, the composition is rinsed from the hair with water, although a weak acid solution may be employed as the rinse.
(~, (? 2011642 One preferred sequence of steps by which colorant formulatlons in accordance with the invention are contacted with human hair involves:
(1) Mix or otherwise prepare dyeing ~olution with oxidant, if ~ppropriate.
(2) Apply developer to the hair.
(3) Rinse.
(4) Shampoo.
(5) Optionally, repeat steps (2)-(4).
SUBSTRATES
-Sub~trates to be colored in accordance with the invention are generally fibrous ones of keratinaceous character. Accordingly, the hair and fur of mammals are typical. Preferred i8 human hair, which hair may be upon a human head (ie., "living" hair) or in a wig, or hair piece.
HLiving~ human hair i8 one highly preferred sUbstrate or surface to be colored.
~ ~! q ~
It should be appreciated that such factors as the porosity, color, etc. of the hair may alter the formulation and/or method of coloring used. Chemically relaxed hair, for example, is highly porous and may not need as high a concentration of colorant and/or as long a contacting time as non-relaxed hair. Similarly, blonde or grey hair may require less rigorous treatment than brown or grey-brown hair because of the lower content of melanin therein.
The following examples will serve to illustrate the invention.
F.xam~les 1 This example describes methods of making various compound set out supra: The overall reaction scheme is:
A. Scheme I
N~z NH2 I~IHz ~,OH [~OCHICHIOH [~,OCHzCH~O~
N01 N02. NOz V
AcN ~ AcN --I HN --02NJ~
2 5 NHAC NHAC r~~2 V
HN --02N J~
~ 2 ~
Compound 7, 7-amino-6-nitro-2H-1,4-benzoxazine, can be prepared in six steps from commercially available 2-amino-5-nitrophenol. O-Alkylation of 1 with 2-haloethanol (BrCH2OH
or ClCH2CH2OH) with base (K2CO3, Na2CO3, KOH, NaOH, etc.) will afford 2. Mesylation of 2 will give the mesylate 3 which can be converted to 7-nitro-2H-1,4-benzoxazine 4. Compound 6 can be prepared by a sequence of reactions:
1) hydrogenation, 2) acetylation, and 3) nitration.
Hydrolysis of 6 with acid will give 7.
B. Scheme II
The key intermediate 4 will be also prepared by the following route. O
- NH2 NHCOCH2CI ' ~
~OH ~,OH ~ O
~JOl ~102. 1~02 The synthesis of 9 is known in the literature (G. Newberg and M.A. Phillips, J. Chem.Soc., 3046, 1928). Reduction of 9 with borane-tetrahydrofuran complex described in the literature (M.E. Jung and J.C. Rohloff, J. Am.Chem.Soc., 50, 4909, 1985) will afford 4. The compound 4 will be further transformed into 7 by the route described in Scheme I.
4 ~
C. Scheme III
NHCOR RCON
~ ~ 7 10 R . CH~. C~H5 11 Compound 4 can be prepared by the procedure described in the literature (G. Coudert, G. Guillaumet, and B. Loubinous, Synthesis, 541, 1979). Compound II can be prepared from 10 by treatment with dibromoethane and base in the presence of a phase-transfer catalyst. Hydrolysis of 11 will give 4.
D. Scheme IV
HN--l RN--l RN --Oj!NJ~ O-N~ O N~
~H~ NHl ~IHCHlCH20H
4-Substituted compounds such as B, C, D and E can be prepared by means of N-alkylation using alkyl halide (CH3I,CH3CH2I, BrCH2CH2)H, BrCH2CH2(0H)CH20H and base (K2CO3, NaOH or KOH, etc.). Selective alkylation of C-7 amino group with alkyl halide (4-position may require protection) will provide F and G. Compound H can be prepared conveniently by treatment of A with ethylene oxide.
X
f i ~? 2011642 Example 1 (Scheme I) 2-(2-Hydroxyethoxy)-4-nitroaniline 2 A mixture of 2-amino-5-nitrophenol (1, 30g), 2-chloroethanol (24.2g) and sodium hydroxide (powdered, 12g) in DMSO (lOOml) was stirred for 2.5 h at llO-C. The mixture was poured onto crushed ice (200g) and the dark yellow precipitate was filtered, washed with H20 three times. Recrystallization from ethanol gave 22.4g (58%) of 2: mp 140-142-C; MS m/e 198 (M+).
2-(2-Mesyloxyethoxy)-4-nitroaniline 3.
To a stirred suspenslon of 2 (42g) and triethylamine (30.4g) in dichloromethane (400 ml) in an ice bath was added dropwise a solution of methanesulfonyl chloride (25.2g) in dichloromethane (100 ml). The mixture was stirred for 30 min. and the precipitate was collected by filtration and recrystallized from ethyl acetate to give 33.77g (58%) of 3: mp 132-135-C; MS m/e 276 (M+).
SUBSTRATES
-Sub~trates to be colored in accordance with the invention are generally fibrous ones of keratinaceous character. Accordingly, the hair and fur of mammals are typical. Preferred i8 human hair, which hair may be upon a human head (ie., "living" hair) or in a wig, or hair piece.
HLiving~ human hair i8 one highly preferred sUbstrate or surface to be colored.
~ ~! q ~
It should be appreciated that such factors as the porosity, color, etc. of the hair may alter the formulation and/or method of coloring used. Chemically relaxed hair, for example, is highly porous and may not need as high a concentration of colorant and/or as long a contacting time as non-relaxed hair. Similarly, blonde or grey hair may require less rigorous treatment than brown or grey-brown hair because of the lower content of melanin therein.
The following examples will serve to illustrate the invention.
F.xam~les 1 This example describes methods of making various compound set out supra: The overall reaction scheme is:
A. Scheme I
N~z NH2 I~IHz ~,OH [~OCHICHIOH [~,OCHzCH~O~
N01 N02. NOz V
AcN ~ AcN --I HN --02NJ~
2 5 NHAC NHAC r~~2 V
HN --02N J~
~ 2 ~
Compound 7, 7-amino-6-nitro-2H-1,4-benzoxazine, can be prepared in six steps from commercially available 2-amino-5-nitrophenol. O-Alkylation of 1 with 2-haloethanol (BrCH2OH
or ClCH2CH2OH) with base (K2CO3, Na2CO3, KOH, NaOH, etc.) will afford 2. Mesylation of 2 will give the mesylate 3 which can be converted to 7-nitro-2H-1,4-benzoxazine 4. Compound 6 can be prepared by a sequence of reactions:
1) hydrogenation, 2) acetylation, and 3) nitration.
Hydrolysis of 6 with acid will give 7.
B. Scheme II
The key intermediate 4 will be also prepared by the following route. O
- NH2 NHCOCH2CI ' ~
~OH ~,OH ~ O
~JOl ~102. 1~02 The synthesis of 9 is known in the literature (G. Newberg and M.A. Phillips, J. Chem.Soc., 3046, 1928). Reduction of 9 with borane-tetrahydrofuran complex described in the literature (M.E. Jung and J.C. Rohloff, J. Am.Chem.Soc., 50, 4909, 1985) will afford 4. The compound 4 will be further transformed into 7 by the route described in Scheme I.
4 ~
C. Scheme III
NHCOR RCON
~ ~ 7 10 R . CH~. C~H5 11 Compound 4 can be prepared by the procedure described in the literature (G. Coudert, G. Guillaumet, and B. Loubinous, Synthesis, 541, 1979). Compound II can be prepared from 10 by treatment with dibromoethane and base in the presence of a phase-transfer catalyst. Hydrolysis of 11 will give 4.
D. Scheme IV
HN--l RN--l RN --Oj!NJ~ O-N~ O N~
~H~ NHl ~IHCHlCH20H
4-Substituted compounds such as B, C, D and E can be prepared by means of N-alkylation using alkyl halide (CH3I,CH3CH2I, BrCH2CH2)H, BrCH2CH2(0H)CH20H and base (K2CO3, NaOH or KOH, etc.). Selective alkylation of C-7 amino group with alkyl halide (4-position may require protection) will provide F and G. Compound H can be prepared conveniently by treatment of A with ethylene oxide.
X
f i ~? 2011642 Example 1 (Scheme I) 2-(2-Hydroxyethoxy)-4-nitroaniline 2 A mixture of 2-amino-5-nitrophenol (1, 30g), 2-chloroethanol (24.2g) and sodium hydroxide (powdered, 12g) in DMSO (lOOml) was stirred for 2.5 h at llO-C. The mixture was poured onto crushed ice (200g) and the dark yellow precipitate was filtered, washed with H20 three times. Recrystallization from ethanol gave 22.4g (58%) of 2: mp 140-142-C; MS m/e 198 (M+).
2-(2-Mesyloxyethoxy)-4-nitroaniline 3.
To a stirred suspenslon of 2 (42g) and triethylamine (30.4g) in dichloromethane (400 ml) in an ice bath was added dropwise a solution of methanesulfonyl chloride (25.2g) in dichloromethane (100 ml). The mixture was stirred for 30 min. and the precipitate was collected by filtration and recrystallized from ethyl acetate to give 33.77g (58%) of 3: mp 132-135-C; MS m/e 276 (M+).
7-Nitro-3,4-dihydro-4H-1,4-benzoxazine 4 .
A mixture of 3 (25g) and potassium hydroxide (7.6g) in DMSO (200 ml) was stirred at 80-C for 2 h and poured onto crushed ice (300g). The resulting yellow precipitate was collected by filtration, washed with water three times and dried under reduced pressure to give 12.8 g (79%) of 4: mp 175-177-C; MS m/e 180 (M~)-4-Acetyl-7-acetamido-3,4-dihydro-2H-1, 4-benzoxazlne 5 A mixture of 4 (8.0g) and 10% Pd-C (0.8g) in ethyl acetate (150 ml) was hydrogenated at 60 p8i for 1 h. The mixture was filtered over Celite into ethyl acetate (50 ml) containing trlethylamine (25 ~1) and acetlc anhydrlde (25 ml) and washed wlth ethyl acetate. After completion of acetylation (usually 1.5 ~), the mixture was washed wlth brlne and water, drled (Na2S04) ~nd evaporated to glve 8.2 g (79%) of 5 as a white solid: mp 150-154-C; MS m/e 234 (M~).
4-Acetyl-7-acetamido-6-nitro-3,4-dihydro-2H-1,4-benzoxazine 6 To a stirred solUtion of 5 (5.0g) ln acetic anhydrid (50 ml) in an ice bath was added 610wly fuming nltr$c acid (5 ml). The mixture was ~tirred for 0.5h and the yèllow precipitate was filtered, washed with water three times and dried under reduced pres~ure to give 4.9g (82%) of 6: mp 199-202-C; MS m/e 279 (M+).
7-Amino-6-nitro-3,4-dihydro-2H-1, 4-benzoxaxine 7.
A mixture of 6 (9.8g) and C-HCl (50 ml) was stirred at 90-C for l.Sh and poured onto crushed ice. The mixture was neutralized with aqueous potassium hydroxide to reach pH 4.6. The dark red solid was collected by filtration, washed three times with H2O
and dried under reduced pressure to give 5.31g (78%) of 7: mp 111-114-C; MS m/e 195 (M+); 'H NMR (DM50-d6) 3.18 (m,2H), 4.19 (m,2H), 5.71 (bs, lH), 6.27 (s,lH), 6.99 (bs,2H) 7.14 (s,lH).
W max 475 m (95~EtOH) (log 3.61).
* Trademal-k ' r 20116~2 Example 2 (Scheme II) 2-Chloroacetamldo-5-nitrophenol 8 To a stirred solution of 1 (18g) in acetone (135 ml) at room temperature was added dropwise a solution of chloroacetyl chloride (10.8 ml) in acetone (10 ml) over a period of 15 min. The mixture was stirred for another 30 min. and poured onto crushed ice (300 g). The white precipitate was collected and washed with H20 to give 9 (24.3g, 90%): mp 233-C; MS m/e 230 (M~).
7-Nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazine ~.
A mixture of 8 (22g) and powdered KOH (6.9g) in DMSO (100 ml) was stirred at 95-C for 30 min. and poured onto crushed ice (400g). The resulting precipitate was collected and washed with H20 to give 9 (15.7gl 85%): mp 230-232-C: MS m/e 194 (M+).
7-Nitro-3,4-dihydro-2H-1,4-benzoxazine 4.
To 9 (lOg) at room temperature was added portionwisQ lM solution of borane-tetrahydrofuran complex (52ml) over a period of 15 min.
The mixture was heated to reflux for 10 min. and poured onto crushed ice (200g). The resulting orange precipitate was collected and washed with water to give 4 (8.9g, 95.9%).
f ~-, 20116~2 Compound 7, produced in ExamplQ 1, was used to color hair as follows:
A co~position was prepared containing:
0.05g : Compound 7 lO.OOg : Water lO.OOg : Ethanol (95%) The composition was used to dye swatches of blended gray hair.
The hair was soaked in the dye 801ution for 30 minutes and then rinsed with water.
The hair was then sub~ected to a 8eries of five 6hampoos and water rinses to determine wa~hfastnesg. The Hunter Tristimulus values of the dyed and shampooed hair are recorded in the table below.
Tristimulus Values L a b Undyed 33.06 -0.47 7.31 Initial 28.31 7.96 7.39 Shampooed 28.38 7.63 7.40 In the Hunter Tristimulus System, "L" is a mea~ure of lightness and darkness, that is, the depth of the color of the hair tress. The lower the value of L, the darker the color.
A decrease ln the value of L indicates a darkening of the hair tress. In the case of bleached and blended gray hair, a lowering of L
shows deposition of hair dye on the tress.
--;) 201~42 The table shows that the blended gray hair tresses were colored to a substantial degree by the dye. Moreover, it i8 ~een that the ~hampooing~ did not significantly increase the values of L in the several tests, indicating good washfastness for the dye.
The ~a" value i8 a measure of the greenness or rednes~ of the hair'~ color. AB the a value ~ncreases, the hair ha~ a more prominent red tonality. A lowering in the a value re~ults in greener 6hades.
The value of "b" i8 a measure of the blueness or yellowness of the hair color. As the b value increases, the hair tress iB more yellow.
Neither the a nor the b values changed significantly due to shampooing.
Based on these results, it is seen that Compound 7 would be very desirable in a semipQrmanent hair dye composition.
Example 4 Hair Dye Composition (Com~osition A) 0.32g : Compound 7 5.OOg : 95% ethanol O.SOg : Hydroxyethyl Cellulose 1.50g : Triethanolamine 88.0Qg : Water 95.32g The composition has a pH of 9.7. When applied for 30 min.
to bleached hair and blended gray hair, this mixture imparts to the hair an orange-red coloration after rinsing and shampooing.
Each shampooing ~tep involved both washing and rinsing.
C ('- 201164~
For comparlson purposes, the following composition (composition B) containing 2-nitro-~-phenylenediamine was ~ormulated.
0.25g : 2-nitro-~-phenylenediamine 5.00g : 95~ ethanol O.50g : Hydroxyethyl Cellulose 1.50g : TriQthanolamine 88.00q : Water 95.25g The composition has a pH o~ 9.7. Bleached and blended gray hair were dyed a~ described in Example 1 to give red coloration.
Hunter Tristimulus Values L a b Compound 7 G 23.65 16.58 8.00 (Compn A) B 22.33 22.98 8.88 2-N02-ppd G 18.08 15.09 6.02 (Compn B) B 20.97 21.11 8.26 G: Blended gray hair B: Bleached hair 20116~2 Example 5 Hair dyeing compositions were made up using the followlng:
Compn. Compn.
C D
Nonoxynol 4 10.50g 10.50 Nonoxynol 9 12.00 12.00 Olelc Acld 2.00 2.00 Propylene Glycol 1.50 1.50 95% Ethanol 5.00 5,00 EPTA 1.25 1.25 Sodium Bisulfite 0.18 0.18 Ammonium Hydroxide 3.25 3.25 Water 13.06 13.17 p-Phenylene~1~mine 0.02 0.02 p-Aminophenol 0.30 0.30 5-Amino-o-cresol 0.43 0.43 Compound 7 0.51 0.00 2-Nitro-~-phenylenediamine O.oO 0.40 Total: 50.00g 50.00g Both compositions have a pH of 9.7.
Hair dye composition C de5cribed above was mixed with 50g of 20 volume hydrogen peroxide. The mixture wa6 allowed to react on bleached and blended gray hair for 30 min. at room temperature. The hair was colored red.
The Composition D containing 2-nitro-~-phenylenediamine rendered hair a red shade, similar to that obtained from C.
F.xample 6 (Dye stability test) This example shows the stability, i.e., non-reactivity of the subject compounds where reaction with monoethanolamine is concerned. A mixture of 7 (0.97g) and monoethanolamine (1.04g) in water (10 ml) was stirred at 110~C for 7 days. The conversion of 14 was not observed.
NH2 tJHCH2CHpH
O ~ O J~
NH ~ N H
7 I~
Under the same conditions, 2-nitro-p-phenylenediamine 1~ underwent nucleophilic substitution with monoethanolamine to give 16. 16 was further converted to 6-aminoquinoxaline 17. See M. Bil and J. Corbett, Dyes and Pigments 2 215, 1981.
NH~ NHCH-CH~OH
NOl ~ N~l ~H2 ~H2 11 Reasonable variations, such as those which would occur to a skilled artisan, can be made herein without departing from the scope of the invention.
. ~
A mixture of 3 (25g) and potassium hydroxide (7.6g) in DMSO (200 ml) was stirred at 80-C for 2 h and poured onto crushed ice (300g). The resulting yellow precipitate was collected by filtration, washed with water three times and dried under reduced pressure to give 12.8 g (79%) of 4: mp 175-177-C; MS m/e 180 (M~)-4-Acetyl-7-acetamido-3,4-dihydro-2H-1, 4-benzoxazlne 5 A mixture of 4 (8.0g) and 10% Pd-C (0.8g) in ethyl acetate (150 ml) was hydrogenated at 60 p8i for 1 h. The mixture was filtered over Celite into ethyl acetate (50 ml) containing trlethylamine (25 ~1) and acetlc anhydrlde (25 ml) and washed wlth ethyl acetate. After completion of acetylation (usually 1.5 ~), the mixture was washed wlth brlne and water, drled (Na2S04) ~nd evaporated to glve 8.2 g (79%) of 5 as a white solid: mp 150-154-C; MS m/e 234 (M~).
4-Acetyl-7-acetamido-6-nitro-3,4-dihydro-2H-1,4-benzoxazine 6 To a stirred solUtion of 5 (5.0g) ln acetic anhydrid (50 ml) in an ice bath was added 610wly fuming nltr$c acid (5 ml). The mixture was ~tirred for 0.5h and the yèllow precipitate was filtered, washed with water three times and dried under reduced pres~ure to give 4.9g (82%) of 6: mp 199-202-C; MS m/e 279 (M+).
7-Amino-6-nitro-3,4-dihydro-2H-1, 4-benzoxaxine 7.
A mixture of 6 (9.8g) and C-HCl (50 ml) was stirred at 90-C for l.Sh and poured onto crushed ice. The mixture was neutralized with aqueous potassium hydroxide to reach pH 4.6. The dark red solid was collected by filtration, washed three times with H2O
and dried under reduced pressure to give 5.31g (78%) of 7: mp 111-114-C; MS m/e 195 (M+); 'H NMR (DM50-d6) 3.18 (m,2H), 4.19 (m,2H), 5.71 (bs, lH), 6.27 (s,lH), 6.99 (bs,2H) 7.14 (s,lH).
W max 475 m (95~EtOH) (log 3.61).
* Trademal-k ' r 20116~2 Example 2 (Scheme II) 2-Chloroacetamldo-5-nitrophenol 8 To a stirred solution of 1 (18g) in acetone (135 ml) at room temperature was added dropwise a solution of chloroacetyl chloride (10.8 ml) in acetone (10 ml) over a period of 15 min. The mixture was stirred for another 30 min. and poured onto crushed ice (300 g). The white precipitate was collected and washed with H20 to give 9 (24.3g, 90%): mp 233-C; MS m/e 230 (M~).
7-Nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazine ~.
A mixture of 8 (22g) and powdered KOH (6.9g) in DMSO (100 ml) was stirred at 95-C for 30 min. and poured onto crushed ice (400g). The resulting precipitate was collected and washed with H20 to give 9 (15.7gl 85%): mp 230-232-C: MS m/e 194 (M+).
7-Nitro-3,4-dihydro-2H-1,4-benzoxazine 4.
To 9 (lOg) at room temperature was added portionwisQ lM solution of borane-tetrahydrofuran complex (52ml) over a period of 15 min.
The mixture was heated to reflux for 10 min. and poured onto crushed ice (200g). The resulting orange precipitate was collected and washed with water to give 4 (8.9g, 95.9%).
f ~-, 20116~2 Compound 7, produced in ExamplQ 1, was used to color hair as follows:
A co~position was prepared containing:
0.05g : Compound 7 lO.OOg : Water lO.OOg : Ethanol (95%) The composition was used to dye swatches of blended gray hair.
The hair was soaked in the dye 801ution for 30 minutes and then rinsed with water.
The hair was then sub~ected to a 8eries of five 6hampoos and water rinses to determine wa~hfastnesg. The Hunter Tristimulus values of the dyed and shampooed hair are recorded in the table below.
Tristimulus Values L a b Undyed 33.06 -0.47 7.31 Initial 28.31 7.96 7.39 Shampooed 28.38 7.63 7.40 In the Hunter Tristimulus System, "L" is a mea~ure of lightness and darkness, that is, the depth of the color of the hair tress. The lower the value of L, the darker the color.
A decrease ln the value of L indicates a darkening of the hair tress. In the case of bleached and blended gray hair, a lowering of L
shows deposition of hair dye on the tress.
--;) 201~42 The table shows that the blended gray hair tresses were colored to a substantial degree by the dye. Moreover, it i8 ~een that the ~hampooing~ did not significantly increase the values of L in the several tests, indicating good washfastness for the dye.
The ~a" value i8 a measure of the greenness or rednes~ of the hair'~ color. AB the a value ~ncreases, the hair ha~ a more prominent red tonality. A lowering in the a value re~ults in greener 6hades.
The value of "b" i8 a measure of the blueness or yellowness of the hair color. As the b value increases, the hair tress iB more yellow.
Neither the a nor the b values changed significantly due to shampooing.
Based on these results, it is seen that Compound 7 would be very desirable in a semipQrmanent hair dye composition.
Example 4 Hair Dye Composition (Com~osition A) 0.32g : Compound 7 5.OOg : 95% ethanol O.SOg : Hydroxyethyl Cellulose 1.50g : Triethanolamine 88.0Qg : Water 95.32g The composition has a pH of 9.7. When applied for 30 min.
to bleached hair and blended gray hair, this mixture imparts to the hair an orange-red coloration after rinsing and shampooing.
Each shampooing ~tep involved both washing and rinsing.
C ('- 201164~
For comparlson purposes, the following composition (composition B) containing 2-nitro-~-phenylenediamine was ~ormulated.
0.25g : 2-nitro-~-phenylenediamine 5.00g : 95~ ethanol O.50g : Hydroxyethyl Cellulose 1.50g : TriQthanolamine 88.00q : Water 95.25g The composition has a pH o~ 9.7. Bleached and blended gray hair were dyed a~ described in Example 1 to give red coloration.
Hunter Tristimulus Values L a b Compound 7 G 23.65 16.58 8.00 (Compn A) B 22.33 22.98 8.88 2-N02-ppd G 18.08 15.09 6.02 (Compn B) B 20.97 21.11 8.26 G: Blended gray hair B: Bleached hair 20116~2 Example 5 Hair dyeing compositions were made up using the followlng:
Compn. Compn.
C D
Nonoxynol 4 10.50g 10.50 Nonoxynol 9 12.00 12.00 Olelc Acld 2.00 2.00 Propylene Glycol 1.50 1.50 95% Ethanol 5.00 5,00 EPTA 1.25 1.25 Sodium Bisulfite 0.18 0.18 Ammonium Hydroxide 3.25 3.25 Water 13.06 13.17 p-Phenylene~1~mine 0.02 0.02 p-Aminophenol 0.30 0.30 5-Amino-o-cresol 0.43 0.43 Compound 7 0.51 0.00 2-Nitro-~-phenylenediamine O.oO 0.40 Total: 50.00g 50.00g Both compositions have a pH of 9.7.
Hair dye composition C de5cribed above was mixed with 50g of 20 volume hydrogen peroxide. The mixture wa6 allowed to react on bleached and blended gray hair for 30 min. at room temperature. The hair was colored red.
The Composition D containing 2-nitro-~-phenylenediamine rendered hair a red shade, similar to that obtained from C.
F.xample 6 (Dye stability test) This example shows the stability, i.e., non-reactivity of the subject compounds where reaction with monoethanolamine is concerned. A mixture of 7 (0.97g) and monoethanolamine (1.04g) in water (10 ml) was stirred at 110~C for 7 days. The conversion of 14 was not observed.
NH2 tJHCH2CHpH
O ~ O J~
NH ~ N H
7 I~
Under the same conditions, 2-nitro-p-phenylenediamine 1~ underwent nucleophilic substitution with monoethanolamine to give 16. 16 was further converted to 6-aminoquinoxaline 17. See M. Bil and J. Corbett, Dyes and Pigments 2 215, 1981.
NH~ NHCH-CH~OH
NOl ~ N~l ~H2 ~H2 11 Reasonable variations, such as those which would occur to a skilled artisan, can be made herein without departing from the scope of the invention.
. ~
Claims (13)
1. Compounds of formula I
(I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyamino-alkyl.
(I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyamino-alkyl.
2. Compounds of claim 1 conforming to formula II:
(II) wherein: R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c, wherein n=1-6 and C=0-3.
(II) wherein: R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c, wherein n=1-6 and C=0-3.
3. Compounds of claim 2 wherein R1 and R2 are both CnH2n+1-c(OH)c groups and c=0-3.
4. Compounds of claim 2 wherein R1 and R2 are both C1-6 alkyl groups.
5. Compounds of claim 2 wherein R1 and R2 are both hydrogen.
6. A composition for dyeing keratinaceous substrates containing in the dye component at least one compound of formula I:
(I) wherein X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
(I) wherein X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
7. The composition of claim 6 wherein the dye component contains at least one compound of formula II:
(II) wherein R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c, wherein n=1-6, and C=0-3.
(II) wherein R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c, wherein n=1-6, and C=0-3.
8. The composition of claim 7 wherein R1 and R2 are both CnH2n+1-c(OH)c groups wherein n=1-6 and C=0-3.
9. The composition of claim 7 wherein R1 and R2 are both C1-6 alkyl groups.
10. The compositions of claim 7 wherein R1 and R2 are both hydrogen.
11. A method of dyeing a keratinaceous substrate comprising the step of contacting the substrate with at least one dye of formula I
(I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
(I) wherein: X and Y are independently selected from the group consisting of: hydrogen, C1-6 alkyl, C1-6 alkoxyalkyl, C1-6 aminoalkyl, C1-6 hydroxyalkyl, and C1-6 hydroxyaminoalkyl.
12. The method of claim 11 wherein the substrate is human hair.
13. The method of claim 12 wherein the dye is of formula II:
(II) wherein: R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c wherein n=1-6, C=0-3.
(II) wherein: R1 and R2 are each independently hydrogen or groups of the formula CnH2n+1-c(OH)c wherein n=1-6, C=0-3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/440,567 US5055110A (en) | 1989-11-22 | 1989-11-22 | Benzoxazine dyes |
| US440,567 | 1989-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2011642A1 CA2011642A1 (en) | 1991-05-22 |
| CA2011642C true CA2011642C (en) | 1997-10-21 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002011642A Expired - Fee Related CA2011642C (en) | 1989-11-22 | 1990-03-07 | Benzoxazine dyes |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US5055110A (en) |
| EP (1) | EP0592396B1 (en) |
| JP (1) | JPH05503091A (en) |
| AR (1) | AR245887A1 (en) |
| AT (1) | ATE151759T1 (en) |
| AU (1) | AU648528B2 (en) |
| BG (1) | BG96367A (en) |
| BR (1) | BR9007862A (en) |
| CA (1) | CA2011642C (en) |
| DE (1) | DE69030511T2 (en) |
| ES (1) | ES2101738T3 (en) |
| FI (1) | FI922324A (en) |
| HU (1) | HUT63397A (en) |
| IE (1) | IE904218A1 (en) |
| MY (1) | MY104777A (en) |
| NO (1) | NO922024L (en) |
| PL (1) | PL287880A1 (en) |
| WO (1) | WO1991007394A1 (en) |
| YU (1) | YU222490A (en) |
| ZA (1) | ZA909310B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420126A (en) * | 1989-11-08 | 1995-05-30 | Yamanouchi Pharmaceutical Co., Ltd. | 3,4-dihydro-2H-1,4-benzoxazine derivatives and pharmaceutical compositions containing the same |
| DE4122035A1 (en) * | 1991-07-03 | 1993-01-07 | Henkel Kgaa | THE USE OF 1,9-DIHYDRO-PYRAZOLO (4,3-B) (1,4) -BENZOXAZINES AS COUPLERS FOR OXIDATION AGENTS |
| US5769901A (en) * | 1996-04-01 | 1998-06-23 | Fishman; Yoram | Powdered hair dye composition and method of application |
| DE19962880A1 (en) * | 1999-12-24 | 2001-06-28 | Henkel Kgaa | Color for coloring keratinous fibers, e.g. hair, wool or fur, especially human hair, contains halogen-substituted benzofurazan or N-oxide compound(s) |
| DE10045599B4 (en) | 2000-09-15 | 2004-06-03 | Wella Ag | Hair dye based on 4-nitro-2,1,3-benzoxadiazole derivatives and its use as a dye for dyeing hair |
| DE10045600A1 (en) * | 2000-09-15 | 2002-04-04 | Wella Ag | Means and processes for dyeing keratin fibers |
| FR3030513B1 (en) * | 2014-12-19 | 2016-12-23 | Oreal | CATIONIC BENZOXAZINE DERIVATIVES AND USE IN CAPILLARY COLORATION. |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA806152A (en) * | 1969-02-11 | Holtzman Harris | Method of dyeing animal fibers | |
| CA935094A (en) * | 1968-02-26 | 1973-10-09 | Halasz Alexander | Nuclear substituted nitroparaphenylenediamines as dyeing compositions |
| LU56703A1 (en) * | 1968-08-13 | 1970-02-13 | ||
| CH614457A5 (en) * | 1975-04-11 | 1979-11-30 | Ciba Geigy Ag | |
| GB8423697D0 (en) * | 1984-09-19 | 1984-10-24 | Ciba Geigy Ag | Benzazole derivatives |
| LU85853A1 (en) * | 1985-04-16 | 1986-11-05 | Oreal | NOVEL NITROAMINOPHENOLS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN DYEING KERATINIC FIBERS, NEW INTERMEDIATE NITROAMINOBENZENES AND THEIR USE IN DYEING KERATINIC FIBERS |
-
1989
- 1989-11-22 US US07/440,567 patent/US5055110A/en not_active Expired - Fee Related
-
1990
- 1990-03-07 CA CA002011642A patent/CA2011642C/en not_active Expired - Fee Related
- 1990-11-19 AT AT91900492T patent/ATE151759T1/en not_active IP Right Cessation
- 1990-11-19 BR BR909007862A patent/BR9007862A/en not_active Application Discontinuation
- 1990-11-19 WO PCT/US1990/006776 patent/WO1991007394A1/en active IP Right Grant
- 1990-11-19 EP EP91900492A patent/EP0592396B1/en not_active Expired - Lifetime
- 1990-11-19 ES ES91900492T patent/ES2101738T3/en not_active Expired - Lifetime
- 1990-11-19 HU HU9201713A patent/HUT63397A/en unknown
- 1990-11-19 JP JP3501077A patent/JPH05503091A/en active Pending
- 1990-11-19 AU AU69021/91A patent/AU648528B2/en not_active Ceased
- 1990-11-19 DE DE69030511T patent/DE69030511T2/en not_active Expired - Fee Related
- 1990-11-20 ZA ZA909310A patent/ZA909310B/en unknown
- 1990-11-21 IE IE421890A patent/IE904218A1/en unknown
- 1990-11-22 AR AR90318440A patent/AR245887A1/en active
- 1990-11-22 YU YU222490A patent/YU222490A/en unknown
- 1990-11-22 MY MYPI90002062A patent/MY104777A/en unknown
- 1990-11-22 PL PL28788090A patent/PL287880A1/en unknown
-
1992
- 1992-05-21 FI FI922324A patent/FI922324A/en unknown
- 1992-05-22 NO NO92922024A patent/NO922024L/en unknown
- 1992-05-22 BG BG096367A patent/BG96367A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HU9201713D0 (en) | 1992-09-28 |
| AU648528B2 (en) | 1994-04-28 |
| US5055110A (en) | 1991-10-08 |
| ATE151759T1 (en) | 1997-05-15 |
| AR245887A1 (en) | 1994-03-30 |
| JPH05503091A (en) | 1993-05-27 |
| BR9007862A (en) | 1992-09-15 |
| FI922324A0 (en) | 1992-05-21 |
| EP0592396B1 (en) | 1997-04-16 |
| ZA909310B (en) | 1991-07-31 |
| HUT63397A (en) | 1993-08-30 |
| NO922024D0 (en) | 1992-05-22 |
| ES2101738T3 (en) | 1997-07-16 |
| YU222490A (en) | 1993-10-20 |
| BG96367A (en) | 1993-12-24 |
| PL287880A1 (en) | 1992-08-24 |
| EP0592396A1 (en) | 1994-04-20 |
| NO922024L (en) | 1992-07-17 |
| AU6902191A (en) | 1991-06-13 |
| WO1991007394A1 (en) | 1991-05-30 |
| CA2011642A1 (en) | 1991-05-22 |
| IE904218A1 (en) | 1991-05-22 |
| MY104777A (en) | 1994-05-31 |
| DE69030511T2 (en) | 1998-01-02 |
| EP0592396A4 (en) | 1992-09-28 |
| DE69030511D1 (en) | 1997-05-22 |
| FI922324A (en) | 1992-05-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |